BACKGROUND OF THE INVENTION
[0001] The present invention relates to a white laminated polyester film and a imaging medium
(recording medium or printing medium), and more particularly, relates to a white laminated
polyester film having excellent surface glossiness and a imaging medium using the
same.
[0002] Recently, an ink jet printing system is rapidly applied to various types of facsimiles,
printers and plotters because of many advantages of this printing system over the
conventional art, such as low noise, capability of high-speed imaging, easy adaptability
to full color printing and low cost.
[0003] On the other hand, by enhancement of printing speed and prevalence of full color
printing retires further improvement in quality of the imaging sheets (recording sheets
or printing sheets) and many studies on the imaging sheets have been made . For instance,
the requirements for the hue b value and surface gloss of the imaging sheet have varied
from the conventional standards for increasing clearness of the printed images, and
similar review is being made on use of synthetic paper or plastic film as imaging
sheet.
[0004] The plastic film used as imaging sheet is usually a white film containing a white
pigment.
[0005] However, with such white films containing a white pigment, although it is possible
to control the hue b value in a satisfactory way when the film is composed of a single
layer, there are limitations on the improvement of surface gloss that can be attained
by use of white pigments, thereby making it difficult to obtain a desired high-gloss
film.
[0006] The imaging layer (recording layer or printing layer) of the imaging sheet applicable
to the ink jet printing system is usually formed by applying on the base film a coating
solution mainly composed of polyvinyl alcohol which is a water-soluble resin.
[0007] Incidentally, the binder resin of the imaging layer is mainly composed of a water-soluble
resin, however, is unsatisfactory in its adhesiveness to the base polyester film,
and it is hardly possible to obtain satisfactory adhesion between the imaging layer
and polyester film even if a known easy-adhering resin layer is provided therebetween.
[0008] As a result of the present inventor's earnest studies to solve the above problems,
it has been found that by laminating a layer of a different polyester on at least
one side of the white polyester film, and further forming thereon an easy-adhering
layer and a imaging layer, the thus obtained white polyester film is free of the above
problems. The present invention has been attained on the basis of the above finding.
SUMMARY OF THE INVENTION
[0009] An object of the present invention is to provide a imaging medium which is capable
of increasing clearness of the printed image, especially when a color image is formed
on a white film.
[0010] Another object of the present invention is to provide a white polyester imaging medium
having remarkably high adhesion between the base white polyester film and the imaging
layer thereon.
[0011] To attain the above aim, in a first aspect of the present invention, there is provided
a white laminated polyester film comprising:
a polyester base film having a transmission density of not less than 0.2 and a hue
b value of the surface thereof of not more than 2; and
an adhesive layer laminated on at least one side of the polyester base film, which
adhesive layer is formed by applying a coating solution comprising a polyvinyl alcohol
resin and a water-soluble resin, a water-dispersible resin or a mixture thereof.
[0012] In a second aspect of the present invention, there is provided a imaging medium comprising
as a substrate the white laminated polyester film as defined in the above first aspect.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present invention is described in detail below.
[0014] This laminated white film comprises a polyester base film and an adhesive layer.
[0015] The polyesters usable for forming the polyester base film according to the present
invention include, for example, polyethylene terephthalate (PET) of which not less
than 80 mol% of the structural units is constituted by ethylene terephthalate; polyethylene-2,6-naphthalate
(PEN) of which not less than 80 mol% of the structural units is constituted by ethylene-2,6-naphthalate;
poly-1,4-cyclohexanedimethylene terephthalate (PCT) of which not less than 80 mol%
of the structural units is constituted by 1,4-cyclohexanedimethylene terephthalate;
polyethylene isophthalate; and polybutylene terephthalate.
[0016] As the other copolymerisation components than the said principal component materials,
there can be used diols such as diethylene glycol, propylene glycol, neopentyl glycol,
1,4-cyclohexanedimethanol, trimethylene glycol, tetramethylene glycol, hexamethylene
glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol and polyalkylene
glycol, and ester-forming derivatives such as isophthalic acid, 2,7-naphthalenedicarboxylic
acid, 5-sodium sulfoisophthalate, oxalic acid, malonic acid, succinic acid, adipic
acid, azelaicacid, sebacic acid, phthalic acid, diphenyl ether dicarboxylic acid and
oxymonocarboxylic acid.
[0017] The polyesters used in the present invention may be either the said single polymers
or copolymers or the blends thereof with small amount of other resins.
[0018] In the present invention, the polyester base film can be produced by, for instance,
the following methods: (1) a method for drawing a composition comprising a polyester
and a white pigment (2) a method for drawing a composition comprising a polyester
and a void-forming agent.
[0019] In the method (1), as the white pigment, there can be used, for example, titanium
oxide, barium sulfate, magnesium oxide, calcium carbonate and the like. The average
particle size of the white pigment is usually 0.05 to 0.5 µm, preferably 0.1 to 0.4
µm. When the average particle size of the pigment is less than 0.05 µm or exceeds
0.5 µm, the produced film may be found too low in transmission density (OD), and the
imaging sheet produced therewith tends to have unsatisfactory light transmission preventive
performance. The amount of the white pigment added is usually 0.5 to 20% by weight,
preferably 1 to 17% by weight. When its amount added is less than 0.5% by weight,
the film is low in transmission density, and the imaging sheet made by using such
a film tends to have poor light transmission preventive effect. On the other hand,
when the amount of the pigment added exceeds 20% by weight, the film is liable to
break during the film forming process, or the formed film may prove too low in mechanical
strength.
[0020] As the white pigment, the titanium dioxide particles having a high opacifying effect
are preferably used in the present invention. The crystal form of such titanium dioxide
particles may be either anatase type or rutile type, but the anatase type is preferred
in terms of hue b value and weather resistance. The titanium dioxide particle surfaces
may have been treated with an oxide of aluminum, silicon, lead and/or an organic compound
for improving dispersibility of the particles in the polyester and their weather resistance.
[0021] In the method (2), the polymers incompatible with the polyesters, such as polyolefins
and polystyrene polymers, are used as the void-forming agent. According to this method,
minute air cells are formed in the film when drawn, giving a low-density white polyester
film. The thus obtained white polyester film resembles paper in weight, rigidity,
hand feeling, etc., unlike the ordinary polyester films of the same thickness.
[0022] The type of the polyolefin used for the said purpose is not specified, but the kind
of polyolefin having a higher modulus of elasticity than the polyester in the temperature
range at the above the glass transition point of the polyester is preferably used
because this type of polyolefin is helpful for forming many minute air cells in the
polyester film. Typical examples of such polyolefin are polyethylene and polypropylene.
The melt flow index of the polyolefin used in the present invention is usually 0.2
to 120, preferably 0.5 to 50.
[0023] The polystyrene polymers usable as void-forming agent in the present invention include
the polystyrene homopolymers obtained by polymerizing the styrene monomers, and the
random, block or graft copolymers mainly composed of the repeating units of styrene
with other monomers. More specifically, they include amorphous polystyrene, crystalline
polystyrene, impact-resistant polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene
copolymer, and the like.
[0024] Examples of other incompatible polymers than those mentioned above include poly-3-methylbutene-1,
poly-4-methylpentene-1, polyvinyl-t-butane, 1,4-trans-poly-2,3-dimethylbutadiene,
polyvinylcyclohexane, polyvinyl-t-butylether, cellulose triacetate, cellulose tripropionate,
polyvinylfluoride, polychlorotrifluoroethylene, and the like. Polyacrylates, polyacryls
and silicone polymers are also usable as incompatible polymer.
[0025] In the composition comprising a polyester and an incompatible polymer, the content
of the polyester is preferably 70 to 98% by weight and the content of the incompatible
polymer is preferably 2 to 30% by weight. When the polyester content is less than
70% by weight, the produced white polyester film tends to have unsatisfactory dimensional
stability. On the other hand, when the incompatible polymer content exceeds 30% by
weight, there may be produced too many air cells, which adversely affect the drawing
properties of the composition. When the incompatible polymer content is less than
2% by weight, formation of the air cells may be insufficient.
[0026] The apparent specific gravity of the white polyester film produced according to the
method (2) mentioned above is usually not less than 0.4, preferably not less than
0.6, even more preferably not less than 0.7. When the apparent specific gravity of
the polyester film is less than 0.4, the cohesive force of the film may lower, and
the cohesive force in the inside of the foamed layer may become smaller than the interfacial
adhesive force between the easy-adhering resin layer and the imaging layer, making
this method unsuited for producing a film which features easy adhesion.
[0027] The white polyester film of the present invention may contain, beside the said polyester
and incompatible polymer, other polymer(s) as a third component in an amount not exceeding
20% by weight, as far as it is not prejudicial to the object of the present invention.
Also, the white film obtained according to the method (2) may contain a white pigment
for increasing its transmission density as in the case of the method (1). As such
a white pigment, in view of the relation between addition density and transmission
density, titanium oxide is preferably used as it contributes to the improvement of
transmission density with a small content. Titanium oxide may be used singly as a
white pigment or in mixture with other type of white pigment.
[0028] The white polyester film according to the present invention may also contain additives
such as fluorescent brightener, colorant, defoaming agent, antistatic agent, antioxidant,
lubricant, anti-blocking agent, ultraviolet absorber and light screen. It may further
contain microfine particles of an inorganic or organic lubricant or the like for improving
slip characteristics of the film.
[0029] The materials of the said microfine particles usable in the present invention include
synthetic silica, kaolin, clay, calcium carbonate, silicon oxide, calcium terephthalate,
aluminum oxide, titanium oxide, calcium phosphate, lithium fluoride, crosslinked polymers,
and high-melting point organic compounds which remain insoluble in melting and film
forming of the polyesters. It is also possible to use the internal particles formed
in the inside of the polymer in the production of the polyester with a metallic compound
catalyst, such as an alkali metal compound or an alkaline earth metal compound, used
in the synthesis of polyesters. Of these materials, synthetic silica is preferred.
The average size of the microfine particles is usually 0.001 to 3.5 µm, and their
content in the film is usually 0.002 to 0.9% by weight.
[0030] Co-extrusion, dry lamination or other methods can be used for producing a white polyester
film in the laminated structure, but the co-extrusion method is preferred. The co-extrusion
method comprises the steps of drying the polyester chips to be used for forming the
layers of the laminate, mixing the additives necessary for the respective layers,
melting and kneading them by the separate extruders, joining the melts in a ply or
in the die head, and extruding the joined material in multiple layers from a die onto
a casting drum (rotary cooling drum) to form a sheet.
[0031] Various types of dryer such as hopper dryer, paddle dryer and vacuum dryer can be
used for drying the polyester chips. T-die method is preferred for extrusion. In casting,
use of the electrostatic pinning technique is preferred.
[0032] The casting drum temperature in the co-extrusion method is preferably set at a somewhat
lower level (at around 70°C or below) than normally required. The thus obtained non-stretched
sheet is stretched in both the machine direction and the transverse direction, and
then heat-set. The sheet is stretched 2.0 to 6.0 times in both directions at a temperature
in the range of (Tg-10)°C to (Tg+50)°C. Heat-setting is preferably conducted in the
temperature range of 150°C to 250°C for 1 second to 5 minutes.
[0033] Heat-setting is usually conducted in a tense fixed state of the film, but the film
may be relaxed or tentered by an amount not exceeding 20% in the longitudinal and/or
transverse direction during heat-setting and/or cooling after heat-setting.
[0034] The polyester base film in the present invention may have a laminated structure,
and a white pigment or an incompatible polymer is contained in at least the polyester
layer constituting the white layer. In case where the white polyester film has a laminated
structure, each of the intermediate layers comprise other polymer than polyester,
as far as the whole structure or the surface layer mainly comprises polyester.
[0035] A white polyester film of a laminated structure can be produced at low cost since
such materials as white pigment, incompatible polymer and particles can be effectively
used for a specific layer alone. Also, in the case of a white polyester film of a
laminated structure, as it is possible to use a laminated structure constituting a
white film and a transparent polyester film selected from the incompatible resin-containing
white polyester film and the white pigment-containing polyester film, the produced
film has both of the innate mechanical and thermal properties of polyester and the
softness and flexibility of the low-density white polyester film.
[0036] The polyester base film comprise a polyester (A) layer and a polyester (B) layer.
The definition of the polyester (A) layer is principally the same definition of the
above described polyester base film.
[0037] The polyester (B) layer is further defined as follows in addition to the definition
of the above described polyester base film.
[0038] The polyester (B) layer in the present invention is subject to no other restrictions
than that it should be a layer of a polyester of the type mentioned above, and that
the 60° glossiness of the surface constituted by the polyester(B) layer should not
be less than 60%. Preferably, it is a polyester layer in which the overall content
of the additives is 0.1 to 1,000 ppm, more preferably 0.1 to 100 ppm. A polyester
layer in which the average dispersal diameter of the additives is 0.01 to 4 µm and
their overall content is 0.1 to 100 ppm, is especially preferred.
[0039] The 60° surface glossiness can be made more than 60% most easily when the thickness
of the polyester (B) layer is not less than 0.5 µm. It is possible to minimize the
influence of the white opacifying layer in the inside on the surface layer of the
film and to sufficiently elevate 60° glossiness of the film surface by making the
polyester (B) layer thickness of not less than 2 µm, preferably not less than 5 µm.
The upper limit of the polyester (B) layer thickness is not defined; it may be properly
decided to meet the conditions for the practical use, under the restriction that the
transmission density (OD) of the film in the final form of laminated film is not less
than 0.2.
[0040] In case where the white laminated polyester film of the present invention is used
as a imaging medium, the transmission density, hue b value and 60° surface glossiness
of the film need to fall within the ranges defined below for obtaining a preferred
color tone of the imaging face (recording face or printing face) and other visual
impressions such as appearance.
[0041] The transmission density (OD) of the white laminated polyester film according to
the present invention is not less than 2, preferably 0.2 to 3, more preferably 0.6
to 3. When the transmission density (OD) is less than 0.2, it is impossible to secure
sufficient opacifying effect as a white film, and the recorded matter in the imaging
layer becomes indistinct. When the transmission density is increased more than necessary,
there may result reduced mechanical strength of the film.
[0042] The hue b value of the surface constituted by the polyester base film of the present
invention is not more than 2, preferably in the range from -10 to 2, more preferably
from -10 to 0. When the hue b value is more than 2, the film surface assumes a slightly
yellowish color tone, making it difficult to attain correct regeneration of color.
When the hue b value is less than -10, the film surfaces takes a slightly bluish color
tone.
[0043] The "hue b value" referred to in the present invention is the b* value of the film
color (ranked as L*, a* and b*) determined according to the indication method (CIE
1976 Lightness) described in JIS Z-8729.
[0044] The 60° glossiness of the surface constituted by the polyester film according to
the present invention is not less than 60%, preferably not less than 80%, more preferably
not less than 100%. By making the 60° surface glossiness of the polyester film not
less than 60%, it is possible to make a imaging medium surface having the impression
of photographic paper, and a imaging face with a sense of high quality can be obtained.
[0045] In case where the white laminated polyester film of the present invention is used
as a imaging medium, a imaging layer is usually formed as a surface functional layer
of the imaging medium. When this imaging layer is provided on the white laminated
polyester film surface, an easy-adhering resin layer is preferably provided as an
undercoat for ensuring high interlaminar adhesion.
[0046] In the present invention, adhesive layer (herein- after referred to as an easy-adhering
resin layer or primer layer) is formed by applying a coating solution containing a
resin comprising a polyvinylalcohol resin and water-soluble or water-dispersible binder
resin on the polyester base film and drying the obtained coat.
[0047] The polyvinyl alcohol resin (herein- after referred to as PVOH resin) contained in
the coating solution used for forming the easy-adhering resin layer in the present
invention can be synthesized by ordinary polymerization reaction. The PVOH resin used
in the present invention is free of restrictions save that it should be soluble in
water. The degree of polymerization of the polyvinyl alcohol resin of the present
invention is not specified, but it is usually not less than 100, preferably selected
from between 300 and 40,000. When the polymerization degree is less than 100, water
resistance of the easy-adhering resin layer may be unsatisfactory. The saponification
degree of the polyvinyl alcohol resin is also not specified, but usually a saponified
product of polyvinyl acetate having a saponification degree of not less than 70 mol%,
preferably 80 to 99.9 mol%, is practically used. The PVOH resin used in the present
invention may be a polyethylene copolymer or a polyvinyl alcohol derivative subjected
to a modification treatment such as acetalation or butyralation treatment, as far
as its main component is polyvinyl alcohol.
[0048] The "water-dispersible binder resin" refers to the resins which don't dissolve but
can be dispersed in water, more specifically the resins which can be forcibly dispersed
in water with the aid of a surfactant.
[0049] As the water-soluble or water-dispersible binder resin, it is preferred to use polyethers
or the self-dispersing type resins having nonionic hydrophilic groups such as hydroxyl
groups or ionic hydrophilic groups (preferably anionic hydrophilic groups).
[0050] The said anionic groups are introduced into the resin through copolymerization or
by other means. Examples of such anionic groups usable in the present invention include
those derived from, for example, sulfonic acid, carboxylic acids, phosphoric acid,
and lithium, sodium, potassium, ammonium and amine salts thereof. The ratio of the
anionic group to the resin solid is usually 0.05 to 8% by weight. When the ratio of
the anionic group is less than 0.05% by weight, water solubility or water dispersibility
of the resin tends to deteriorate. On the other hand, when the ratio of the anionic
group exceeds 8% by weight, water resistance of the easy-adhering resin layer may
lower, making this resin layer more liable to absorb moisture, resulting in greater
probability of blocking of the white polyester films having the said easy-adhering
resin layer.
[0051] As the said binder resin, at least one type of resin selected from the group consisting
of water-soluble or water-dispersible polyester resins, polyurethane resins and acrylic
resins is preferably used.
[0052] The said water-soluble or water-dispersible polyesters can be synthesized from an
ordinary polycondensation reaction of a polyvalent carboxylic acid and a polyvalent
hydroxyl compound such as shown below.
[0053] Examples of the polyvalent carboxylic acids usable for the above reaction include
terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic
acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic
acid, 2-potassiumsulfoterephthalic acid, 5-sodiumsulfoisophthalic acid, adipic acid,
azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutalic acid, succinic acid,
trimellitic acid, trimesic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic
acid, trimellitic acid monopotassium salt, and their ester forming derivatives.
[0054] Examples of the polyvalent hydroxyl compounds include ethylene glycol, 1,2-propylene
glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol,
neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylene glycol, bisphenol A-ethylene
glycol addition product, diethylene glycol, triethylene glycol, polyethylene glycol,
polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol,
dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate,
sodium dimethylolpropionate, and potassium dimethylolpropionate.
[0055] The said polyurethanes can be synthesized from an ordinary polymerization reaction
using as starting materials a polyol, a polyisocyanate, a chain extender and a crosslinking
agent.
[0056] The polyols usable for the above reaction include polyethers such as polyoxyethylene
glycol, polyoxypropylene glycol, polyoxypropylenetriol and polyoxytetramethylene glycol;
polyesters such as polyethylene adipate, polyethylenebutylene adipate, polypropylene
adipate, polyhexylene adipate and polycaprolactone; acrylic polyols; and castor oil.
[0057] The polyisocyanates usable for the said reaction include aromatic diisocyanates such
as tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate
and 1,5-naphthalene diisocyanate, and aliphatic diisocyanates such as xylene diisocyanate,
hexamethylene diisocyanate, lysine diisocyanate, 4,4'-dicyclohexylmethane diisocyanate
and isophorone diisocyanate.
[0058] As the chain extender or crosslinking agent, there can be used, for example, ethylene
glycol, propylene glycol, butanediol, hexanediol, diethylene glycol, trimethylolpropane,
glycerin, hydrazine, ethylenediamine, diethylenetriamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodicyclohexylmethane and water.
[0059] The said acrylic resins can be synthesized by means of ordinary copolymerization
using, for instance, an alkyl acrylate or methacrylate (A component) and a vinyl monomer
(B component) copolymerizable therewith, and having a functional group. The ratio
of the component A to the total amount of the components A and B is usually 30 to
90 mol%, and the ratio of the component B is usually 10 to 70 mol%.
[0060] The vinyl monomer which has a functional group and is compolymerizable with the alkyl
acrylate or methacrylate and is preferably the one having such a functional group
that can impart hydrophilicity to the acrylic resin to better its water dispersibility
while enhancing adhesion of the acrylic resin to the white polyester film or to the
image on the imaging layer provided on an easy-adhering resin layer, and that can
also better hydrophilicity of the acrylic resin in cooperation with the polyester
blended in the easy-adhering resin layer.
[0061] Preferred examples of such functional groups include carboxyl groups and salts thereof,
acid anhydride groups, sulfonic groups and salts thereof, amide groups or alkylolated
amide groups, amino groups (including substituted amino groups) or alkylolated amino
groups and salts thereof, hydroxyl groups and glycidyl groups. Carboxyl groups or
salts thereof, acid anhydride groups and glycidyl groups are preferred. Two or more
types of these groups may be contained in the acrylic resin.
[0062] The acrylic resins in which the copolymerization percentage of the alkyl acrylate
and/or alkyl methacrylate is not less than 30 mol%, have good coatability and can
provide a strong coating film and excellent anti-block properties. By regulating the
content of the alkyl acrylate and/or alkyl methacrylate in the acrylic resin to be
not more than 90 mol%, it is possible to enhance water solubility or dispersibility
of the compound having a specific functional group with introduction of the acrylic
resin and to maintain this condition stably over a long period of time. It is also
possible to better adhesion of the white polyester film to the easy-adhering resin
and to realize improvement of strength, water resistance and chemical resistance of
the easy-adhering resin layer through reaction in this layer.
[0063] The alkyl group in the said alkyl acrylate and alkylmethacrylate may be, for instance,
methyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, lauryl, stearyl or cyclohexyl.
[0064] As the said vinyl monomer, those having a functional group such as reactive functional
group, self-crosslinking functional group or hydrophilic group can be used. Examples
of such vinyl monomers include alkali metal salts or alkaline earth metal salts of
acrylic acid, methacrylic acid, itaconic acid, maleic acid or the like, ammonium salts,
and maleic anhydride.
[0065] Examples of the vinyl monomers having an amide group or a alkylolated amide group
include acrylamide, methacrylamide, N-methylmethacrylamidle, methylolated acrylamide,
methylolated methacrylamide, ureidovinyl ether, β-ureidoisobutylvinyl ether, and ureidoethyl
acrylate.
[0066] Examples of the vinyl monomers having an amino group or a alkylolated amino group
or a salt thereof include diethylaminoethylvinyl ether, 2-aminoethylvinyl ether, 3-aminopropylvinyl
ether, 2-aminobutylvinyl ether, dimethylaminoethyl methacrylate, dimethylaminoethylvinyl
ether, the vinyl monomers having the said amino groups methylolated, and the vinyl
monomers quaternized with a halogenated alkyl, dimethylsulfuric acid, sultone or the
like.
[0067] Examples of the vinyl monomers having a hydroxyl group are β-hydroxyethyl acrylate,
β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate,
β-hydroxyvinyl ether, 5-hydroxypentylvinyl ether, hydroxyhexylvinyl ether, polyethylene
glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate,
polypropylene glycol monomethacrylate.
[0068] Examples of the vinyl monomers having a glycidyl group are glycidyl acrylate and
glycidyl methacrylate.
[0069] Also, the said acrylic resins may be properly blended with acrylonitrile, styrenes,
butylvinyl ether, maleic acid mono- or di-alkyl ester, fumaric acid mono- or di-alkyl
ester, itaconic acid mono- or di-alkyl ester, methyl vinyl ketone, vinyl chloride,
vinylidene chloride, vinyl acetate, vinylpyridine, vinylpyrrolidone, vinyltrimethoxysilane
or the like as copolymer component.
[0070] The said acrylic resins may contain surfactant(s) mixed therein in the production
process. However, in case where a polyester resin and/or a polyurethane resin are
jointly used as a binder resin, when the ratio of the acrylic resin to such a binder
resin is high, the low-molecular weight surfactant contained in the acrylic resin
is concentrated in the film-forming process, and consequently, it is accumulated at
the interface of the particles and forced to migrate to the interface of the easy-adhering
resin layer to adversely affect its mechanical strength, water resistance and adhesiveness.
In such a case, it is preferred to use an acrylic resin containing no surfactant,
obtained by so-called soap-free polymerization.
[0071] An acrylic resin containing no surfactant can be produced by using the methods such
as disclosed in Comprehensive Technical Data on Water-Soluble Polymers and Water-Dispersible
Resins," page 309, published by Keiei Kaihatsu Center, January 1981, and a lecture
meeting text: An Outlook on Future from the Results of Latest Studies - New Development
of Emulsions and Their Technical Problems in Future (December 1981), Industrial Technology
Research Society
[0072] More specifically, the method using an oligomer or a high-molecular weight surfactant
instead of a low-molecular weight surfactant; the method using a polymerization initiator
such as potassium persulfate or ammonium persulfate for introducing a hydrophilic
group into the polymer; the method in which the monomers having a hydrophilic group
are copolymerized; the method using a reactive surfactant; the method of producing
a core-shell polymer by changing the textures of the inside layer and the outside
layer of the disperse phase; and other relating methods can be used for producing
the water-dispersible acrylic resins containing no surfactant.
[0073] As the water soluble resin or water-dispersible resin, polyglycerol glycidyls are
also preferably used.
[0074] Polyglycerol glycidyl may be contained in the coating solution used for forming the
easy-adhering resin layer in the present invention. The polyglycerol polyglycidyl
ether used in the present invention is synthesized from, for example, polyether glycerin
and epichlorohydrin. Its average molecular weight is not specified, but it is usually
not more than 1,200, preferably 250 to 1,000. When the average molecular weight of
this substance is more than 1,200, its water solubility lowers to such a degree that
this substance may be not preferable for use in forming an agueous coating solution.
If its average molecular weight is too small, adhesiveness of the easy-adhering resin
layer may lower. The glycidyl compounds usable as a component of the said substance
have at least two, preferably three or more glycidyl groups, and at least one, preferably
two or more hydroxyl groups in the molecule. These functional groups may undergo intermolecular
or intra molecular glycidyl/hydroxyl condensation reaction by heat in the easy-adhering
resin layer.
[0075] In forming the easy-adhering resin layer in the present invention, a water-soluble
or water-dispersible binder resin other than those mentioned above may be jointly
used, if required. For instance, an epoxy resin or an amide resin can be used as such
an additional binder resin. The skeletal structure of such a resin may be substantially
a composite structure formed by copolymerization. Examples of the binder resins having
a composite structure include acrylic resin grafted polyesters, acrylic resin grafted
polyurethanes, vinyl resin grafted polyesters, and vinyl resin grafted polyurethanes.
[0076] The easy-adhering resin layer may have a component which reacts with the reactive
functional group contained in the binder resin. As such reactive component, there
can be used, for instance, methylolated or alkylolated urea-based, melamine-based,
guanamine-based, acrylamide-based and polyamide-based compounds, polyamines, epoxy
compounds, oxazoline compounds, aziridine compounds, block isocyanate compounds, silane
coupling agents, titanium coupling agents, zirco-aluminate-based coupling agents,
metal chelates, organic acid anhydrides, organic peroxides, heat- or light-reactive
vinyl compounds and photosensitive resins.
[0077] The said reactive component may be either a low-molecular weight compound or a high
polymer having the reactive functional groups as far as at least two reactive functional
groups are contained in one molecule in the binder resin. Use of this reactive component
contributes to the improvement of anti-block properties, water resistance, solvent
resistance and mechanical strength of the easy-adhering resin layer.
[0078] The inactive particles may be contained in the easy-adhering resin layer for improving
its slip properties. As such inactive particles, it is possible to use the inorganic
particles such as particles of colloidal silica, alumina, calcium carbonate, titanium
oxide and the like, and the organic particles such as particles of polystyrene resins,
polyacrylic resins and polyvinyl resins. The average diameter (d) of these inactive
particles is selected within the range of usually L/3 to 3L, preferably L/2 to 2L,
where L is the average thickness of the easy-adhering resin layer.
[0079] A coating solution containing the said binder resin as essential component and the
said reactive component and hydrophilic inactive particles as optional components
is used.
[0080] The coating solution used for forming an easy-adhering resin layer on at least one
side of the white polyester film is usually prepared by using water as a main medium
of the coating solution for reasons of safety and hygienic effect. The coating solution
may contain a small quantity of an organic solvent for the purpose of bettering water
dispersibility or improving the film-forming properties, as far as water is used as
the main medium. It is preferable that the organic solvent is used in such an amount
that is wholly dissolved in water used as the main medium.
[0081] The organic solvents usable for the above purpose include aliphatic or alicyclic
alcohols such as n-butyl alcohol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol
and methyl alcohol; glycols such as propylene glycol, ethylene glycol and diethylene
glycol; glycol derivatives such as n-butyl cellosolve, ethyl cellosolve, methyl cellosolve
and propylene glycol monomethyl ether; ethers such as dioxane and tetrahydrofuran;
esters such as ethyl acetate and amyl acetate; ketones such as methyl ethyl ketone
and acetone; and amides such as N-methylpyrrolidone.
[0082] The method for forming the easy-adhering resin layer on the white polyester film
surface is not specified in the present invention, but preferably a method is used
in which a coating solution of an easy-adhering resin is applied in the polyester
film producing process. Specifically, the following methods are suggested: the coating
solution is applied on the surface of a non-stretched sheet and dried; the coating
solution is applied on the surface of a monoaxially stretched film and dried; or the
coating solution is applied on the surface of a biaxially stretched film and dried.
Of these methods, the method in which the coating solution is applied on the surface
of a monoaxially stretched film and dried and hardened in the heat-treatment of the
film is preferred economically.
[0083] It is also possible to combine two or more of the said coating methods. For instance,
the first layer of easy-adhering resin is coated on the surface of a non-stretched
sheet and dried, then the sheet is monoaxially stretched, and the second layer of
easy-adhering resin is coated thereon and dried. In the present invention, it is preferable
from the aspect of production cost to use a method in which the coating solution is
applied on a monoaxially stretched film, and after dried or in a still undried state,
the coated film is stretched in the direction orthogonal to the previous monoaxial
stretching.
[0084] As means for applying the coating solution of an easy-adhering resin on the surface
of a white polyester film, various coating devices such as reverse roll coater, gravure
coater, rod coater, air doctor coater, etc., shown in Y. Harasaki: Coating Systems,
1979, Maki Shoten, can be used.
[0085] The easy-adhering resin layer may be formed either on one side alone or on both sides
of the white polyester film. In case where the said resin layer is formed on one side
alone, a layer different from the easy-adhering resin layer may be formed on the opposite
side to afford an additional property to the support for the imaging sheet of the
present invention. Before coating, the film may be subjected to a chemical treatment
or a discharge treatment for improving applicability and adhesion of the coating solution
to the film. Also, a discharge treatment may be conducted after formation of the easy-adhering
resin layer for further improving the surface properties of the imaging sheet support.
[0086] The dry thickness of the easy-adhering resin layer is usually 0.01 to 0.5 µm, preferably
0.02 to 0.3 µm. When the easy-adhering resin layer thickness is less than 0.01 µm,
the "easy adhering" properties of the resin may not be sufficiently attained, and
when the layer thickness exceeds 0.5 µm, the produced film tends to show poor blocking
resistance. The problem of blocking may be serious in case where an easy-adhering
resin layer is formed on both sides of the film.
[0087] The easy-adhering resin layer may be formed either on one side alone or on both sides
of the white polyester film. In case where it is formed on one side alone of the film,
a layer different from the easy-adhering resin layer may be formed on the opposite
side to impart an additional property to the support for the imaging sheet of the
present invention. Before coating, the film may be subjected to a chemical or discharge
treatment for improving coatability and adhesion of the coating solution to the film.
It is also possible to perform a discharge treatment after forming the easy-adhering
resin layer for further improving the surface characteristics of the imaging sheet
support.
[0088] The imaging medium of the present invention is constituted by forming a imaging layer
on the easy-adhering resin layer. The imaging layer can be formed by a conventional
method. For instance, in case of an application to the ink jet printing system, the
imaging layer can be formed by applying a water/alcohol mixed solvent solution containing
the additives, for example, a hydrophilic binder resin such as polyvinyl alcohol resin,
a crosslinking agent, colloidal silica, etc.
[0089] The imaging layer according to the present invention can be formed by a conventional
method using a preferable coating device such as mentioned above. The thickness of
this imaging layer may be properly selected in conformity to the image forming system
employed. For instance, in the case of the ink jet printing system, the imaging layer
thickness is set to be at least 1 to 50 µm for use in the known printing apparatus
for allowing the aqueous ink to be absorbed quickly in the vertical direction to minimize
repulsion or blotting of the agueous ink. By further defining the imaging layer thickness
to be 3 to 50 µm, preferably 5 to 30 µm, it is possible to facilitate absorption of
the aqueous ink, which is an important factor for obtaining clear prints with little
blotting of the ink.
[0090] The imaging medium of the present invention is constituted by forming a imaging layer
mainly composed of a water-soluble resin on the easy-adhering resin layer. The water-soluble
resin used for forming the imaging layer is, for instance, selected from the resins
mainly composed of polyacrylic acid, polyvinyl alcohol or the like, polyvinyl alcohol
being preferred. The water-soluble resin used in the present invention may have been
copolymerized with other resins or subjected to a modification treatment such as acetalation
or butyralation treatment, as far as it has a water-soluble resin substance as main
component in the molecule. However, if such copolymerization or modification treatment
goes so far that the water-soluble resin substance becomes unable to serve as main
component, it becomes hardly possible for the imaging layer to maintain water holdability
required for the printing operation, such as ink jet printing, and the formed image
lacks clearness.
[0091] Other additives such as crosslinking agent and colloidal silica are preferably contained
in the imaging layer of the present invention. Particularly, containing colloidal
silica is preferable as it helps to form appropriate spaces in the imaging layer to
facilitate absorption of the ink on the imaging layer surface just after printing
(such as ink jet printing), thus expediting apparent drying of the imaging layer.
[0092] Imaging on the imaging layer in the present invention can be effected by a method
described as information imaging system (recording system or printing system) in "Market
of Printer Peripheral Materials and Chemicals", CMC (1996). The current information
imaging system is roughly divided into digital imaging system and analog imaging system,
which are further classified into electrophotographic system, thermosensitive system,
ink jet system, electrostatic electrography, magnetography, photo-imaging system,
etc. The imaging layer of the present invention can adapt itself to any of these imaging
systems and is preferred for the imaging media where a water-soluble resin is used
as a main component, but its use is not limited to these applications. It is possible
to apply the aqueous ink by the other methods. For instance, writing with an aqueous
pen is within the scope of the present invention.
[0093] According to the present invention, as described above, it is possible to obtain
a white laminated polyester film with excellent opacifying properties, good hue and
high glossiness, and a high-quality imaging medium capable of forming the clear images
is provided by using this film.
EXAMPLES
[0094] The present invention is described in further detail by showing the examples thereof,
but it should be understood that these examples are merely intended to be illustrative
and not to be construed as limiting the scope of the invention in any way. The evaluation
methods used in the Examples and Comparative Examples are as described below. All
"parts" and "percents (%)" in the Examples and Comparative Examples are by weight
unless otherwise noted.
(1) Measurement of laminate thickness
[0095] Laminate thickness was measured by observing the sectional photographs of the sample
films using a scanning electron microscope (SEM) S4500 (mfd. by Hitachi Ltd.). Measurement
was conducted at 10 points, and the average of the 10 measurements was shown here.
(2) Transmission density (OD)
[0096] Transmitted light density (OD) through a G filter was measured using a Macbeth densitometer
"TD-904". The higher the value of the transmitted light density, the higher is the
opacifying power. Measurement was made at 3 points, and the average of the 3 measurements
was given. Transmission density (OD) was evaluated according to the following criterion.
- ⓞ (excellent):
- OD≧1.0
- ○ (good):
- 0.6≦OD<1.0
- △ (fair):
- 0.2≦OD<0.6
- X (poor):
- OD<0.2
[0097] In the present invention, ⓞ, ○ and △ are preferable.
(3) Hue b value
[0098] Using a color analyzer (TC-1800 MK-II mfd. by Tokyo Denshoku KK), the surface of
the (B) layer of the white laminated ((A) layer + (B) layer) polyester film was measured
according to the method of JIS Z-8722, and the film color (L*, a*, b*) was determined
according to the indication method (CIE 1976 Lightness) described in JIS Z-8729, with
the b* value given here as hue b value. The higher the b* value on the + side, the
stronger is the yellowish tint. Measurement was made at 3 points, and the average
of the 3 measurements was given. Color evaluation was made according to the following
criterion. Hereinafter, the "b* value" is indicated as "b value" for convenience'
sake.
- ⓞ (excellent):
- b value<-1
- ○ (good):
- -1≦b value<0
- △ (fair):
- 0≦b value<2
- X (poor):
- 2≦b value:
[0099] In the present invention, ⓞ, ○ and △ are preferable. (4) 60° glossiness
[0100] Light was applied to the (B) layer surface of the white laminated ((A) layer + (B)
layer) polyester film, and specula glossiness was measured with the incident light
having no polarization according to the method of JIS Z-8741 using a varied-angle
glossimeter (VGS-1001DP mfd. by Nippon Denshoku KK). Measurement was made at 3 points,
and the average of the 3 measurements was given. 60° glossiness was evaluated according
to the following criterion.
- ⓞ (excellent):
- glossiness≧100
- ○ (good):
- 80≦glossiness<100
- △ (fair):
- 60≦glossiness<80
- X (poor):
- 60>glossiness
[0101] In the present invention, ⓞ, ○ and △ are preferable.
(5) Adhesion of imaging layer
[0102] Black-color printing was conducted (over the area of 12 cm x 12 cm) on the imaging
layer surface by an ink jet printer (BJC-600JF mfd. by Canon Corp.) and air dried
(23°C, 50% RH) for about 12 hours or more. Cellotape (18 mm wide adhesive tape, produced
by Nichiban Co., Ltd.) was pasted on the printed surface and peeled off quickly. The
state and result of peeling was visually observed and evaluated according to the following
criterion.
- ○ (good):
- Peeled less than 20%
- △ (fair):
- Peeled 20% to less than 80%
- X (poor):
- Peeled 80% or more
[0103] In the present invention, ○ and △ are preferable.
[0104] The details of the adhesive resin layer and the imaging layer in Examples 1 to 8
are as described below.
〈Easy-adhering resin layer〉
[0105] A coating solution (a 5% water dispersion) prepared by mixing a binder resin (1)
(a polyester resin mainly composed of isophthalic acid, ethylene glycol and neopentyl
glycol, with a carboxylate being introduced as water-dispersing functional group),
polyvinyl alcohol (2) (saponified approximately 94%), polyglycerol glycidyl ether
(3) and inactive silica particles (4) (average particle size = 55 nm) in a mixing
ratio of (1):(2):(3):(4) = 35:35:25:5 was applied on the base film and dried to form
an about 0.5 µm thick easy-adhering resin layer.
〈Imaging layer〉
[0106] A coating solution (an 8% water/isopropanol solution) comprising a polyvinylalcohol
resin whose hydroxyl groups are partially modified to acetal (S-LEC KX-1: degree of
acetalation (8±3 mol%) produced by Sekisui Chemical Co., Ltd.) was applied on the
easy-adhering resin layer and dried to form an about 8 µm thick imaging layer for
ink jet printing.
Example 1
[0107] 100 parts of dimethyl terephthalate and 60 parts of ethylene glycol were supplied
as starting materials into a reactor with 0.09 part of magnesium acetate tetrahydrate
as catalyst. The reaction was started at 150°C, and the temperature was gradually
raised while causing evaporation of methanol till reaching 230°C in 3 hours.
[0108] 4 hours after start of the reaction, the ester exchange reaction was substantially
completed. To this reaction mixture were added 0.04 part of ethyl acid phosphate and
0.04 part of antimony trioxide for 4.5-hour polycondensation reaction. The temperature
was gradually elevated from 230°C till reaching 280°C, while pressure was gradually
reduced from normal pressure till finally reaching 0.3 mmHg. The reaction was terminated
on the elapse of 4.5 hours after start of the reaction, and the polymer was discharged
out of the reactor under nitrogen pressure. The obtained polyester had an intrinsic
viscosity of 0.65.
[0109] This polymer was subjected to solid phase polymerization under the conditions of
225°C and 0.3 mmHg to obtain a polyester (A1) having an intrinsic viscosity of 0.81.
This polyester (A1) was blended with various types of additive in the ratios shown
in Table 1 by a vented twin-screw extruder to obtain the polyesters (A2)-(A4).
Table 1
Polyester type |
Additive |
Additive content |
Particle size (µm) |
A1 |
None |
- |
- |
A2 |
Titanium dioxide |
40% |
0.3 |
A3 |
Amorphous silica |
3% |
3.5 |
A4 |
Amorphous silica |
1% |
2.4 |
A5 |
Fluorescent brightener (OB-1)* |
1% |
- |
* OB-1: trade name (produced by Eastman Kodak Co.) |
[0110] These polyesters A1-A4 were uniformly blended in the ratios shown in Table 2 to obtain
the starting polyester materials.
Table 2
Starting polyester material |
Polyester type |
|
A1 |
A2 |
A3 |
A4 |
A5 |
W1 |
50 |
30 |
16 |
- |
4 |
W2 |
66 |
30 |
- |
- |
4 |
T1 |
99 |
- |
- |
1 |
- |
[0111] Polyester material W1 for forming the polyester (A) layer and polyester material
T1 for forming the polyester (B) layer were dried at 180°C for 4 hours, then melted
by an extruder set at 285°C, extruded from a multi-layer die into a two-layer laminated
sheet form, and rapidly cooled and solidified on a casting drum (rotary cooling drum)
set at a surface temperature of 30°C utilizing the electrostatic pinning cooling technique
to obtain a substantially amorphous sheet about 370 µm thick.
[0112] This amorphous sheet was stretched 3.0 times in the machine direction at 83°C, then
a coating solution for forming the said easy-adhering resin layer was applied on the
surface of the polyester (B) layer, and the coated sheet was further stretched 3.1
times in the transverse direction at 120°C and then heat treated at 230°C for 6 seconds
to obtain an approximately 40 µm thick biaxially stretched white polyester film having
the specified easy-adhering resin coating layer.
[0113] The final thickness of the polyester (B) layer laminated by using a multi-layer die
was as shown in Table 3 below.
[0114] Then a coating solution for forming the said imaging layer was applied by a bar coater
on the surface of the easy-adhering resin layer formed on the polyester (B) layer
surface to make a imaging medium for ink jet printing. The properties of the thus
obtained imaging medium were evaluated, the results being shown in Table 4.
Examples 2-4
[0115] The same procedure as defined in Example 1 was conducted except that the thickness
of the polyester (B) layer was changed as shown in Table 3 to obtain the biaxially
stretched white polyester films and the imaging media for ink jet printing, and their
properties were evaluated. The results are shown in Table 4.
Examples 5-8
[0116] The same procedure as defined in Example 1 was conducted except that the polyester
material W2 was used for forming the polyester (A) layer, and that the thickness of
the polyester(B) layer was changed as shown in Table 3, to obtain the biaxially stretched
white polyester films and the imaging media for ink jet printing, and their properties
were evaluated. The results are shown in Table 4.
Table 3
|
Polyester material |
(B) layer thickness (µm) |
|
(A) layer |
(B) layer |
|
Example 1 |
W1 |
T1 |
0.53 |
Example 2 |
W1 |
T1 |
1.71 |
Example 3 |
W1 |
T1 |
3.68 |
Example 4 |
W1 |
T1 |
9.15 |
Example 5 |
W2 |
T1 |
0.82 |
Example 6 |
W2 |
T1 |
1.85 |
Example 7 |
W2 |
T1 |
3.12 |
Example 8 |
W2 |
T1 |
8.00 |
Table 4
|
Transmission density |
(B) layer side |
Adhesion |
|
|
Hue b value |
60° glossiness |
|
Example 1 |
ⓞ |
ⓞ |
△ |
○ |
Example 2 |
ⓞ |
ⓞ |
△ |
○ |
Example 3 |
ⓞ |
ⓞ |
○ |
○ |
Example 4 |
ⓞ |
ⓞ |
ⓞ |
○ |
Example 5 |
ⓞ |
ⓞ |
○ |
○ |
Example 6 |
ⓞ |
ⓞ |
ⓞ |
○ |
Example 7 |
ⓞ |
ⓞ |
ⓞ |
○ |
Example 8 |
ⓞ |
ⓞ |
ⓞ |
○ |
〈Easy-adhering resin layer〉
[0117] The easy-adhering resin layers of Examples 9-16 and Comparative Examples 1-8 were
obtained using the coating solutions prepared by blending the following resins (C-F)
in the ratios shown in Table 5 below.
(C) A resin mainly comprising polyvinyl alcohol having a degree of saponification
of about 94% and an average molecular weight of 500.
(D) A water-soluble or water-dispersible resin.
(D1) A polyester mainly comprising isophthalic acid, ethylene glycol and neopentyl
glycol, with a carboxylate introduced as water-dispersing functional group.
(D2) A polyurethane comprising as main components a polyester diol mainly comprising
terephthalic acid, isophthalic acid and ethylene glycol, isophorone diisocyanate and
dimethylolpropionic acid, and dispersed with a carboxylate.
(E) Polyglycerol polyglycidyl ether having an average molecular weight of about 750.
(F) Inactive particles having an average size of 0.05 µm.
Table 5
|
C |
D1 |
D2 |
E |
F |
Example 9 |
50 |
45 |
|
|
5 |
Example 10 |
50 |
|
45 |
|
5 |
Example 11 |
35 |
35 |
|
25 |
5 |
Example 12 |
35 |
|
35 |
25 |
5 |
Example 13 |
60 |
|
35 |
|
5 |
Example 14 |
45 |
45 |
|
5 |
5 |
Example 15 |
30 |
60 |
|
5 |
5 |
Example 16 |
20 |
20 |
|
55 |
5 |
Comparative Example 1 |
95 |
|
|
|
5 |
Comparative Example 2 |
|
95 |
|
|
5 |
Comparative Example 3 |
|
|
95 |
|
5 |
Comparative Example 4 |
|
|
|
95 |
5 |
Comparative Example 5 |
|
50 |
|
45 |
5 |
Comparative Example 6 |
|
50 |
45 |
|
5 |
Comparative Example 7 |
|
35 |
35 |
25 |
5 |
Comparative Example 8 |
60 |
|
|
35 |
5 |
〈Imaging layer〉
[0118] A imaging layer for ink jet printing formed by applying a coating solution (an 8%
water/isopropanol solution) comprising a polyvinylalcohol resin whose hydroxyl groups
are partially modified to acetal (S-LEC KX-1 degree of acetalation (8±3 mol%) produced
by Sekisui Chemical Co., Ltd.), the coating thickness being about 8 µm. The said polyvinyl
acetal resin is polyvinyl alcohol having a degree of acetalation of about 8 mol%.
Example 9
[0119] 100 parts of dimethyl terephthalate and 60 parts of ethylene glycol were supplied
as starting materials into a reactor with 0.09 part of magnesium acetate as catalyst.
The reaction was started at 150°C, and the temperature was gradually raised while
causing evaporation of methanol until reaching 230°C in 3 hours.
[0120] 4 hours after start of the reaction, the ester exchange reaction was substantially
completed. To this reaction mixture were added 0.04 part of ethyl acid phosphate and
0.04 part of antimony trioxide for 4.5-hour polycondensation reaction. The temperature
was gradually raised from 230°C till reaching 280°C, while the pressure was gradually
reduced from normal pressure till finally reaching 0.3 mmHg. The reaction was stopped
on the elapse of 4.5 hours from the start of the reaction, and the produced polymer
was discharged out of the reactor under nitrogen pressure. The obtained polyester
had an intrinsic viscosity of 0.65.
[0121] This polymer was subjected to solid phase polymerization under the conditions of
225°C and 0.3 mmHg. The resultantly obtained polyester R1 had an intrinsic viscosity
of 0.81. This polyester R1 was dried and blended with various types of additive in
the ratios shown in Table 6 below using a vented twin-screw extruder to obtain the
polyesters R2-R4.
Table 6
Polyester type |
Additive |
Additive content |
Particle size (µm) |
R1 |
None |
|
|
R2 |
Titanium dioxide |
40% |
0.3 |
R3 |
Amorphous silica |
3% |
3.5 |
R4 |
Fluorescent brightener (OB-1)* |
1% |
|
* OB-1: trade name (produced by Eastman Kodak Co. Ltd.) |
[0122] The polyesters R1-R4 were uniformly blended in a ratio of R1:R2:R3:R4 = 50:30:16:4
to obtain a white polyester material.
[0123] This white polyester material was dried at 180°C for 4 hours, melted by an extruder
set at 285°C, extruded from a single-layer die into a sheet, and rapidly cooled and
solidified on a casting drum (rotary cooling drum) set at a surface temperature of
30°C using the electrostatic pinning cooling technique to obtain an approximately
370 µm thick, substantially amorphous sheet.
[0124] This amorphous sheet was stretched 3.0 times in the machine direction at 83°C, then
a coating solution for forming the said easy-adhering resin layer was applied on the
polyester surface, and the coated sheet was further stretched 3.1 times in the transverse
direction at 120°C, and finally heat-treated at 230°C for 6 seconds to obtain an approximately
40 µm thick biaxially stretched white polyester film having the specified easy-adhering
resin coating layer.
[0125] Then a coating solution for forming the said imaging layer was applied on the surface
of the easy-adhering resin layer by a bar coater to make a imaging medium for ink
jet printing, and its properties were evaluated. The results are shown in Table 11.
Examples 10-16 and Comparative Examples 1-8
[0126] The same procedure as defined in Example 9 was conducted except that the solid content
of the resin forming the easy-adhering resin layer in the coating solution was changed
as shown in Table 6 to obtain the biaxially stretched white polyester films and the
imaging media for ink jet printing, and their properties were evaluated. The results
are shown in Table 7.
Table 7
|
Transmission density |
Imaging face b value |
Adhesion |
Example 9 |
ⓞ |
ⓞ |
△ |
Example 10 |
ⓞ |
ⓞ |
△ |
Example 11 |
ⓞ |
ⓞ |
○ |
Example 12 |
ⓞ |
ⓞ |
○ |
Example 13 |
ⓞ |
ⓞ |
△ |
Example 14 |
ⓞ |
ⓞ |
○ |
Example 15 |
ⓞ |
ⓞ |
○ |
Example 16 |
ⓞ |
ⓞ |
△ |
Comparative Example 1 |
ⓞ |
ⓞ |
X |
Comparative Example 2 |
ⓞ |
ⓞ |
X |
Comparative Example 3 |
ⓞ |
ⓞ |
X |
Comparative Example 4 |
ⓞ |
ⓞ |
X |
Comparative Example 5 |
ⓞ |
ⓞ |
X |
Comparative Example 6 |
ⓞ |
ⓞ |
X |
Comparative Example 7 |
ⓞ |
ⓞ |
X |
Comparative Example 8 |
ⓞ |
ⓞ |
X |